Dr. Jeffrey Mighion
"Selective Functionalization of Carbon-Hydrogen Bonds"
Carbon-hydrogen bonds (C–H bonds) are ubiquitous in organic molecules and the selective conversion of these C–H bonds into carbon-carbon, carbon-nitrogen, carbon-oxygen, and other types of bonds is a major area of chemical research within the organic community.1 Utilization of C–H bonds as synthetic handles to build molecular complexity is a challenge due to the number of C–H bonds present in organic compounds and their usually low reactivity, yet is also rewarding as this allows for utilization of cheap, renewable starting materials and simplification of synthetic strategy.2 There are three main classes of reactions that many of the C–H functionalization strategies fall into:1) C–H activation by generation of an organometallic species from a C–H bond; 2) group transfer chemistry which usually takes place at an electrophilic low-valent ligand on the metal (i.e. carbenoid, nitrenoid, oxo); and 3) homolytic cleavage, C– H abstraction or radical methodology. Our research over the REU summer focuses on the second class of reactions, group transfer chemistry. Specifically, how do we create these reactive metalloids and how can we utilize and access new metalloid species?
REU students will synthesize new organometallic catalyst, test their ability to catalyze group transfer reactions and explore the reactivity of these new catalysts with the goal of developing novel and useful reactivity. The use of modern organic laboratory chemistry skills, spectroscopy, and synthetic design will be taught over the course of the REU.
1) (a) Davies, H. M. L.; Manning, J. R. Nature 2008, 451, 417. (b) Lewis, J. C.; Bergman, R. G.; Ellman, J. A. Acc. Chem. Res. 2008, 41, 1013. (c) Zhang, S.-Y.; Zhang, F.-M.; Tu, Y.-Q Chem. Soc. Rev. 2011, 40, 1937. (d) Newhouse, T.; Baran, P. S. Angew. Chem. Int. Ed. 2011, 50, 3362. (e) Zalatan, D. N.; Du, B. J Top. Curr. Chem. 2010, 292, 347. (f) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147. (g) Davies, H. M. L.; Morton, D. J. Org. Chem. 2016, 81, 343.
2) (a) Brückl, T.; Baxter, R. D.; Ishihara, Y.; Baran, P. S. “Acc. Chem. Res. 2012, 45, 826. (b) Gutekunst, W. R.; Baran, P. S. Chem. Soc. Rev. 2011, 40, 1976. (c) Davies, H. M. L.; Denton, J. R. Chem. Soc. Rev. 2009, 38, 3061. (d) Godula, K.; Sames, D. Science, 2006, 312, 67.